Synthesis, structure and theoretical simulation of a zinc(II) coordination complex with 2,3-pyridinedicarboxylate

Abstract

Hydrolytic opening reaction of 2,3-pyridine dicarboxylic anhydride with the zinc dichloride led to form the chelate complex of mono deprotonated 2,3-pyridine dicarboxylic acid, [Zn(2,3-pdcH)2(H2O)2], (2,3-pdcH = 2,3-pyridinedicarboxylic acid). The coordinated compound crystallizes in the monoclinic space group P21/n. The crystal structure of the title compound exhibits a homoleptic complex with distorted octahedral geometry and ligand coordinated via pyridine nitrogen and oxygen atoms from one deprotonated dicarboxylic acid. Intermolecular interactions were analysed by Hirshfeld surfaces. After formation of the metal complex, the crystal packing is stabilized by O-H…O and C-H…O hydrogen bonds. There are moreover hydrophobic interactions, which consist in stacking between the pyridine cycle and the carboxylic/carboxylate groups. NBO and QTAIM analyses have been performed to evaluate the charge delocalization interactions that occur between the Zn(II) central ion and the surrounding ligand donor atoms. The HOMO and LUMO energies and Molecular Electrostatic Potential surface were derived from DFT theoretical calculations. Keywords Zn(II) chelate complex • Hirshfeld surface • Metal-Ligand interaction • 2,3pyridinedicarboxylate ligand • DFT

Computational (DFT) and Experimental (NMR) Study of the Chelation of an Iridium Hyperpolarization Transfer Catalyst by Amino Acids

“…The energy of frontier orbitals (HOMO-Highest Occupied Molecular Orbital and LUMO -Lowest Unoccupied Molecular Orbital) plays an important role in defining the chemical reactivity descriptors and chemical behaviour of chemical compounds. [38] For all chiral amino acid complexes in this study, the LUMO is mainly localized on the pyridine co-substrate while the HOMO is primarily localized on the metal centre (Figure 10). The energy gaps between the frontier orbitals of the three binding modes increase in magnitude in the order (3) < (1) < (2) with ΔE = 3.51, 3.57, 3.66 eV respectively for the alanine complexes, ΔE = 3.51, 3.58, 3.63 eV for the valine complexes, and ΔE = 3.51, 3.58, 3.66 eV for the glycine complexes.…”

“…The Berny algorithm was first designed by Schlegel et al [37] and has gone through several improvements over the years. [38] For the interconversions involving binding modes (1) and (3) the calculations optimized to a higher energy state accompanied by a single distinct imaginary frequency. These higher energy states were confirmed to be transition states by integrating the intrinsic reaction coordinates (IRCs).…”

“…The energy of frontier orbitals (HOMO‐Highest Occupied Molecular Orbital and LUMO – Lowest Unoccupied Molecular Orbital) plays an important role in defining the chemical reactivity descriptors and chemical behaviour of chemical compounds [38] . For all chiral amino acid complexes in this study, the LUMO is mainly localized on the pyridine co‐substrate while the HOMO is primarily localized on the metal centre (Figure 10).…”

Ultratrace Aromatic Anhydride Dopant as Intermediate Island to Promote Charge Transfer of Graphitic Carbon Nitride for Enhancing the Photocatalytic Degradation of Rhodamine B

“…To our knowledge, 2,3-pyridinedicarboxylic anhydride (PDA) was first selected as a bifunctional dopant for modification of g-C 3 N 4 , because it has the highly reactive anhydride groups and a conjugated pyridine ring. PDA is a commercial intermediate for organic synthesis, and its typical conversion to the corresponding amide products is obtained by ammonia hydrolysis of the anhydride groups of PDA. − The reactivity of the anhydride groups of PDA ensures that it is easily integrated into g-C 3 N 4 , and superconjugation of the solitary pair of electrons of the nitrogen atoms of PDA regulates the electron cloud of g-C 3 N 4 to facilitate charge transport. Based on the analysis results of enhancing carrier transfer by doping PDA, using a bifunctional dopant that would effectively form an extended coplanar conjugated system to modify g-C 3 N 4 can yield significant carrier transport performance.…”